New Coolant Compositions
A novel coolant composition with low electrical conductivity and enhanced corrosion inhibition addresses safety and corrosion issues in internal combustion engines and new energy vehicles by combining antifreezing agents, azole derivatives, inorganic salts, and organosilicon compounds.
Patent Information
- Application Number
- PCT/CN2025/084096
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2024-08-05
- Filing Date
- 2025-03-21
- Publication Date
- 2025-10-02
AI Technical Summary
Conventional coolant compositions for internal combustion engines and new energy vehicles exhibit high electrical conductivity, posing safety risks due to potential short-circuits and thermal runaway, and fail to effectively inhibit corrosion across various metallic materials.
A novel coolant composition comprising antifreezing agents, azole derivatives, inorganic salts, organosilicon compounds, and organic amines, which together provide low electrical conductivity and enhanced corrosion inhibition, especially for ferrous and aluminium-containing alloys.
The coolant achieves low electrical conductivity (5-500 μS/cm) suitable for both internal combustion engines and new energy vehicles, reducing the risk of thermal runaway and ensuring effective corrosion protection across diverse materials.
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Figure PCTCN2025084096-FTAPPB-I100001 
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Figure PCTCN2025084096-FTAPPB-I100003
Abstract
Description
New Coolant CompositionsDescription
[0001] The present invention relates to novel coolant compositions based on freezing point-lowering liquids as main constituent, specific alkoxy aminoalkylsilane organic compounds as corrosion inhibitors, and also further corrosion inhibitors which are different therefrom.
[0002] Coolant compositions for the cooling apparatuses (which are usually configured as cooling circuits) of Internal Combustion Engines (ICE) for automobiles and stationary platforms, for example, automobiles usually comprise alkylene glycols such as monoethylene glycol (MEG) or monopropylene glycol (MPG) , optionally in admixture with glycerol, as antifreeze component which lowers the freezing point of the coolant composition. Apart from further components such as antifoams, dyes or bitter substances, corrosion inhibitors, in particular, are comprised.
[0003] Especially in modern ICE, temperatures which place severe demands on the materials used are reached. Any type and any extent of corrosion represent a potential risk factor which can lead to shortening of the life of the engine and to a decrease in reliability. Furthermore, a number of different materials, for example cast iron, copper, brass, soft solder, steel and also aluminium, aluminium alloys and magnesium alloys, are increasingly being used in modern engines. This plurality of metallic materials additionally results in potential corrosion problems, in particular at the places where different metals are in contact with one another. Various types of corrosion such as pit corrosion, crevice corrosion, erosion or cavitation can occur comparatively easily at such places in particular. The coolant compositions likewise have to be compatible with nonmetallic constituents of the cooling apparatuses, for example elastomers and plastics from hose connections or seals, and must not change these. Furthermore, the type of coolant composition is of critical importance for heat transfer in modern ICE. These requirements for the cooling apparatuses of ICE are also applicable for the cooling apparatuses of New Energy Vehicle (NEV) . In principle, NEV can be classified as Battery Electrical Vehicle (BEV) , Hybrid Electrical Vehicle (HEV) , Plug-in Hybrid Electrical Vehicle (PHEV) , Ranger Extender Electrical Vehicle (REEV) , Fuel Cell Electrical Vehicle (FCEV) , etc.,
[0004] In addition, conventional engine coolants (electrical conductivity between 3000-6000 μs / cm at 25 ℃) are being widely used in the cooling apparatuses of NEV. However, in some conditions like battery package failure, car crash and so on, these coolants may close contact with battery cell. Under the voltage of 400V or even 800V of the vehicle platform in the future, the water / glycol based conventional coolants can readily result in short-circuits, also can be easily electrolyzed to generate Hydrogen (flammable) and Oxygen (in favor of flame) , which could lead to thermal runaway, fire even explosion finally. Additionally, battery, E-motor and control unit in stationary platforms like battery swap stations, charging stations, etc. will also meet the same safety issues that need to be taken care of in certain scenarios. Low Electrical Conductivity Coolant (LECC) is believed to alleviate the risk of thermal runaway and other dangerous scenarios.
[0005] EP 2956520 B1 discloses coolant concentrates comprising –inter alia –contain 2-thiothiazole derivatives bearing a carboxyalkyl radical.
[0006] Such sulphur-containing inhibitors provide excellent inhibition of aluminium corrosion even in the presence of potassium fluoroaluminates.
[0007] However, it is a disadvantage that the coolants according to EP 2956520 B1 exhibit a high electrical conductivity.
[0008] Therefore, it was an object of the present invention to provide coolant compositions with a lower electrical conductivity than the coolants according to EP 2956520 B1 but maintaining the corrosion inhibition activity of those coolants.
[0009] Preferably, the coolants according to the invention are expect to fulfil the general requirements according to ASTM D3306, inter alia the corrosion test according to ASTM D1384 or equivalent Chinese National standard GB 29743.1-2022 as well as GB 29743.2-20XX (Published in Jan. 2024 for public opinion) .
[0010] The object was achieved by novel coolants (coolant compositions) , comprising
[0011] (A) at least one antifreezing agent selected from the group consisting of 1, 2-ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, glycerol, dimers, trimers or oligomers thereof, and mono-or dialkyl ethers thereof
[0012] (B) water
[0013] (C2) at least one azol derivative different from (C1) ,
[0014] (C1) optionally additionally to azol derivative (C2) at least one 2-thiothiazole of the general formula (I)
[0015] where the variable R1 is a carboxyalkyl radical of the formula - (CmH2m) -COOX, where m is from 1 to 4 and X is hydrogen, an alkali metal cation, an ammonium cation or a substituted ammonium cation, and the variables R2 and R3 are each, independently of one another, hydrogen or a C1-C4-alkyl group, where R2 and R3 together with the two ring carbon atoms of the thiazole ring to which they are attached may also form a five-or six-membered saturated or unsaturated ring,
[0016] (D) optionally at least one inorganic salt as further corrosion inhibitor selected from the group consisting of molybdates, borates, silicates, vanadates, tungstates, inorganic phosphate salts and antimonates,
[0017] (E) at least one organosilicon compound comprising at least one alkoxy aminoalkylsilane (E3) and optionally additionally at least one further organosilicon compound selected from the group consisting of
[0018] -esters of orthosilicic acid (E1) and
[0019] -alkoxy alkylsilanes (E2) ,
[0020] (F) optionally at least one aliphatic, cycloaliphatic or aromatic monocarboxylic, dicarboxylic or tricarboxylic acid as acid or in the form of alkali metal, ammonium or substituted ammonium salts thereof having from 3 to 21 carbon atoms in the acid part, preferably at least one monocarboxylic acid combined with one dicarboxylic acid, and
[0021] (G) optionally at least one organic amine.
[0022] It is an advantage of the present coolants that they exhibit not only low electrical conductivity but also a high inhibition of corrosion, especially corrosion of ferrous-and aluminium-containing alloys, and non-ferrous-alloys.
[0023] The amines (G) preferably have 2 to 9, especially 4 to 8 carbon atoms. The amines (G) are preferably tertiary amines, preferably contain 0 to 3 ether oxygen atoms or 0 to 3, preferably 0 to 2 hydroxyl groups.
[0024] Target electrical conductivity according to ASTM D 1125 at 25 ℃ of such coolants (as 50%Ready-To-Use , RTU aqueous solution) is preferably between 5-500 μS / cm, preferably between 5-300 μS / cm , preferably between 5-200 μS / cm, preferably between 5-100 μS / cm , preferably between 10-100 μS / cm, preferably between 15-100 μS / cm, preferably between 20-100 μS / cm, preferably between 25-100 μS / cm, preferably between 30-100 μS / cm, preferably between 35-100 μS / cm, more preferably between 40-100 μS / cm, very particularly preferably between 45-100 μS / cm or between 50-100 μS / cm.
[0025] Such low electrical conductivity makes the coolants according to the present invention suitable not only for cooling systems of ICE, but also for cooling systems of NEV. Appropriate application scenarios of automobiles are battery, E-motor, control units and engine if there is one in BEV, HEV, PHEV, REEV and FCEV and so on. In addition, potential application scenarios also include stationary platforms whereas ICE, battery, E-motor and control unit are used.
[0026] Indeed, the coolants according to the present invention address the challenges faced by car manufacturers in the design of thermal management systems for HEV / PHEV as well as solve the problems during the construction and retrofitting of coolant refuelling lines, i.e., chemicals compliance, cost pressures and so on. It brings remarkable economic benefits and has far-reaching practical significance and great historical significance.
[0027] In some embodiments, the coolants (coolant compositions) comprise at least one of above components (D) , (F) and (G) ; preferably components (D) and (F) ; more preferably components (D) , (F) and (G) .
[0028] For example, in some preferable embodiments, the coolants (coolant compositions) comprise
[0029] (A) at least one antifreezing agent selected from the group consisting of 1, 2-ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, glycerol, dimers, trimers or oligomers thereof, and mono-or dialkyl ethers thereof
[0030] (B) water
[0031] (C2) at least one azol derivative different from (C1) ,
[0032] (C1) optionally additionally to azol derivative (C2) at least one 2-thiothiazole of the general formula (I)
[0033] where the variable R1 is a carboxyalkyl radical of the formula - (CmH2m) -COOX, where m is from 1 to 4 and X is hydrogen, an alkali metal cation, an ammonium cation or a substituted ammonium cation, and the variables R2 and R3 are each, independently of one another, hydrogen or a C1-C4-alkyl group, where R2 and R3 together with the two ring carbon atoms of the thiazole ring to which they are attached may also form a five-or six-membered saturated or unsaturated ring,
[0034] (D) at least one inorganic salt as further corrosion inhibitor selected from the group consisting of molybdates, borates, silicates, vanadates, tungstates, inorganic phosphate salts and antimonates, preferably molybdates,
[0035] (E) at least one organosilicon compound comprising at least one alkoxy aminoalkylsilane (E3) and optionally additionally at least one further organosilicon compound selected from the group consisting of
[0036] -esters of orthosilicic acid (E1) and
[0037] -alkoxy alkylsilanes (E2) ,
[0038] (F) at least one aliphatic, cycloaliphatic or aromatic monocarboxylic, dicarboxylic or tricarboxylic acid as acid or in the form of alkali metal, ammonium or substituted ammonium salts thereof having from 3 to 21 carbon atoms in the acid part, preferably at least one monocarboxylic acid combined with one dicarboxylic acid, and
[0039] (G) at least one organic amine.
[0040] With the addition of components D, F and G, the coolant is more preferable, as it further shows excellent corrosion inhibition against ferrous-containing alloys (e.g. cast iron) , which makes it more suitable for the cooling systems of ICE.
[0041] The compounds of the coolants according to the invention are described in more details:
[0042] (A) Antifreezing agent
[0043] As antifreezing agent (A) according to the present invention one or more compounds selected from the group consisting of 1, 2-ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, glycerol or dimers, trimers or oligomers thereof or mono-or dialkyl ethers thereof are used.
[0044] Preference is given to 1, 2-ethylene glycol or 1, 2-propylene glycol or dimers, trimers or oligomers thereof or mono-or dialkyl ethers thereof.
[0045] Special preference is given to 1, 2-ethylene glycol or 1, 2-propylene glycol, especially 1, 2-ethylene glycol.
[0046] Preferably 1, 2-propylene glycol and its derivatives is used. Derivatives of 1, 2-propylene glycol may be poly-and oligomers as well as mono-or dialkyl ethers of 1, 2-propylene glycol, its poly-and oligomers.
[0047] More preferably 1, 2-ethylene glycol and its derivatives is used. Derivatives of 1, 2-ethylene glycol may be poly-and oligomers as well as mono-or dialkyl ethers of 1, 2-ethylene glycol, its poly-and oligomers. Examples are diethylene glycol, triethylene glycol, diethylene glycol mono C1-C4 alkyl ether, and triethylene glycol mono C1-C4 alkyl ether, even more preferably 1, 2-ethylene glycol, diethylene glycol, and triethylene glycol, most preferably 1, 2-ethylene glycol or diethylene glycol, and especially 1, 2-ethylene glycol.
[0048] Dimers, trimers or oligomers of the alkylene glycols mentioned are di alkylene glycols, tri alkylene glycols, tetra alkylene glycols as well as higher homologues thereof up to a molecular weight of 598 g / mol.
[0049] Preference is given to the monomeric alkylene glycols and their dimers or trimers, more preferred are the monomeric alkylene glycols and their dimers, special preference is given to the monomeric alkylene glycols.
[0050] Mono-or dialkyl ethers of the above-mentioned alkylene glycols and their poly-and oligomers are preferably mono-or di-C1-to C4-alkyl ethers, more preferably mono-C1-to C4-alkyl ethers, even more preferably methyl-, ethyl-or n-butyl ethers, especially mono-methyl-, ethyl-or n-butyl ethers.
[0051] In the context of the present text the phrase "C1-to C4-alkyl" stands for methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl, preferably methyl, ethyl, n-propyl, n-butyl, iso-butyl, and tert-butyl, more preferably methyl, ethyl, and n-butyl.
[0052] Preferably compounds (A) are selected from the group consisting of monoethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol and mixtures thereof, 1, 3-propanediol, higher poly alkylene glycols, alkylene glycol ethers, for example monoethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, monoethylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monoethyl ether, monoethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol mono-n-butyl ether and tetraethylene glycol mono-n-butyl ether or glycerol, in each case either alone or as mixtures thereof.
[0053] Preferably compound (A) is 1, 2-ethylene glycol or 1, 2-propylene glycol, especially 1, 2-ethylene glycol.
[0054] (B) Water
[0055] Water used for the coolants according to the present invention should be ion-free, designating water with a neutral pH-value and comprising essentially no further ions than those hydroxide ions and hydronium ions out of the autoprotolysis of water at the respective temperature.
[0056] The electrical conductivity (throughout this text determined according to ASTM D 1125) at 25 ℃of the ion-free water used should preferably not exceed 5 μS / cm, more preferably not more than 3, even more preferably not more than 2, and especially not more than 1 μS / cm.
[0057] The ion-free water used can be pure distilled or twice-distilled water or water which has been deionized, for example by ion exchange, preferably by ion exchange of at least its cations, more preferably by ion exchange of both cations and anions.
[0058] Water from osmosis can also be used in the coolants according to the present invention.
[0059] (C) Azol derivatives
[0060] The coolants according to the present invention comprise at least one azol derivative (C2) different from (C1) (both see below) and may optionally comprise at least one 2-thiothiazole (C1) additionally to azol derivative (C2) .
[0061] (C1) 2-Thiothiazole
[0062] The at least one 2-thiothiazole (C1) of the general formula (I)
[0063] where the variable R1 is a carboxyalkyl radical of the formula - (CmH2m) -COOX, where m is from 1 to 4 and X is hydrogen, an alkali metal cation, an ammonium cation or a substituted ammonium cation, and the variables R2 and R3 are each, independently of one another, hydrogen or a C1-C4-alkyl group, where R2 and R3 together with the two ring carbon atoms of the thiazole ring to which they are attached may also form a five-or six-membered saturated or unsaturated ring.
[0064] Preference is given to the benzothiazoles of the general formula (III)
[0065] where
[0066] the variable R is hydrogen or a C1-C10-alkyl radical, in particular methyl or ethyl, and
[0067] the variable R' is -S-R1.
[0068] Preferred are (2-benzothiazylthio) acetic acid (R = H, R'= -S-CH2-COOH) or (2-benzothiazylthio) propionic acid (R = H, R'= -S-CH2-CH2-COOH) , especially (2-benzothiazylthio) acetic acid.
[0069] (C2) Azol derivative different from (C1)
[0070] The coolants according to the invention comprise at least one azol derivative (C2) different from (C1) .
[0071] Azole derivatives in the context of the present description mean five-membered heterocyclic compounds having 2 or 3 heteroatoms from the group consisting of nitrogen and sulphur and comprise no or at most one sulphur atom and can bear an aromatic or saturated six-membered fused-on ring.
[0072] These five-membered heterocyclic compounds (azole derivatives) usually contain two N atoms and no S atom, 3 N atoms and no S atom or one N atom and one S atom as heteroatoms.
[0073] Preferred groups of the specified azole derivatives are annellated imidazoles and annellated 1, 2, 3-triazoles of the general formula
[0074] where
[0075] the variable R is hydrogen or a C1-C10-alkyl radical, in particular methyl or ethyl, and
[0076] the variable X is a nitrogen atom or the C-H group.
[0077] Typical and preferred examples of azole derivatives of the general formula (1) are benzimidazole (X = C-H, R = H) , benzotriazoles (X = N, R = H) and tolutriazole (tolyltriazole) (X = N, R = CH3) . A typical example of an azole derivative of the general formula (2) is hydrogenated 1, 2, 3-tolutriazole (tolyltriazole) (X = N, R = CH3) .
[0078] A further preferred group of the specified azole derivatives is benzothiazoles of the general formula (3)
[0079] where
[0080] the variable R is as defined above and
[0081] the variable R' is hydrogen, a C1-C10-alkyl radical, in particular methyl or ethyl, or in particular a mercapto group (-SH) . A typical example of an azole derivative of the general formula (3) is 2-mercaptobenzothiazole.
[0082] Further suitable azole derivatives are non-annellated azole derivatives of the general formula (4)
[0083] where
[0084] the variables X and Y together are two nitrogen atoms or
[0085] one nitrogen atom and a C-H group,
[0086] for example 1 H-1, 2, 4-triazole (X = Y = N) or preferably imidazole (X = N, Y = C-H) .
[0087] For the purposes of the present invention, benzimidazole, benzotriazole, tolutriazole, hydrogenated tolutriazole or mixtures thereof, in particular benzotriazole or tolutriazole, are very particularly preferred as azole derivatives.
[0088] (D) Inorganic salt
[0089] The coolants according to the present invention may further comprise, preferably do further comprise at least one inorganic salt (D) .
[0090] The inorganic salt (D) is at least one inorganic salt as further corrosion inhibitor selected from the group consisting of molybdates, silicates, borates, vanadates, tungstates, inorganic phosphate salts, and antimonates, preferably selected from the group consisting of molybdates, silicates, borates, inorganic phosphate salts, and vanadates, even more preferably selected from the group consisting of molybdates, inorganic phosphate salts, and silicates, and especially are molybdates.
[0091] Inorganic phosphate salt may be used in the form of the alkali metal, ammonium or substituted ammonium salts of orthophosphoric acid H3PO4 or the acid itself, where alkali metal, ammonium or substituted ammonium salts have the meanings indicated above. However, the component will generally be present entirely or predominantly in salt form in the coolant of the invention which normally has a pH of from 4 to 11, in particular from 7 to 11. When free orthophosphoric acid is used, this is usually converted by means of sodium or potassium hydroxide, ammonia or appropriate amines into the desired salts. Further suitable components are alkali metal, ammonium or substituted ammonium salts of diphosphoric acid, of metaphosphoric acids, of pyrophosphoric acids and / or of polyphosphoric acids or the acids themselves, where alkali metal, ammonium or substituted ammonium salts have the meanings indicated above. It is also possible to use mixtures of the salts and / or acids mentioned. Typical representatives of such phosphates are sodium dihydrogenphosphate, disodium hydrogenphosphate, trisodium phosphate, sodium diphosphate, tetrasodium pyrophosphate, sodium tripolyphosphate, sodium hexametaphosphate and the analogous potassium salts.
[0092] As molybdate it is usual to use the alkali metal, ammonium or substituted ammonium salts of molybdic acid H2MoO4 or the acid itself, where alkali metal, ammonium or substituted ammonium salts have the meanings indicated above. Typical representatives of such molybdates (D) are sodium molybdate and potassium molybdate.
[0093] Inorganic silicates are sodium or potassium salts of the group consisting of orthosilicates (SiO44-) , metasilicates (SiO32-) , and pyrosilicates (Si2O76-) .
[0094] Borates are usually used in the form of sodium tetraborate (borax) .
[0095] (E) Organosilicon Compounds
[0096] The coolants according to the present invention comprise at least one Organosilicon Compounds, and the Organosilicon Compounds comprising at least one alkoxy aminoalkylsilane (E3) . Furthermore, the coolants optionally additionally may comprise at least one further organosilicon compound selected from the group consisting of
[0097] -esters of orthosilicic acid (E1) and
[0098] -alkoxy alkylsilanes (E2) .
[0099] In one embodiment, the coolants comprise at least one alkoxy aminoalkylsilane (E3) without the presence of any further silicon-containing compounds.
[0100] In another embodiment, the coolants comprise at least one alkoxy aminoalkylsilane (E3) in combination with an ester of orthosilicic acid (E1) .
[0101] (E1) Esters of orthosilicic acid are compounds of the formula
[0102] Si (OR5) 4
[0103] wherein
[0104] R5 is an organic substituent comprising 1 to 6 carbon atoms, for example a linear or branched, preferably a linear alkyl substituent comprising 1 to 6 carbon atoms or an aromatic substituent comprising 6 carbon atoms, more preferably an alkyl substituent comprising 1 to 4 carbon atoms and even more preferably an alkyl substituent comprising 1 or 2 carbon atoms.
[0105] (E2) Alkoxy alkylsilanes are less preferred and both the alkoxy substituent as well as the alkyl group comprise a linear or branched, preferably a linear alkyl substituent comprising 1 to 6 carbon atoms, more preferably an alkyl substituent comprising 1 to 4 carbon atoms and even more preferably an alkyl substituent comprising 1 or 2 carbon atoms.
[0106] Typical examples of compounds are tetraalkoxysilanes, preferably tetramethoxysilane and tetraethoxysilane, and alkoxyalkylsilanes, preferably triethoxymethylsilane, diethoxydimethylsilane, ethoxytrimethylsilane, trimethoxymethylsilane, dimethoxydimethylsilane and methoxytrimethylsilane. Preference is given to tetraalkoxysilanes, particularly preferably tetramethoxysilane and tetraethoxysilane, with very particular preference being given to tetraethoxysilane.
[0107] (E3) Alkoxy Aminoalkylsilanes
[0108] One type of E3) Alkoxy Aminoalkylsilanes are the compounds of the formula
[0109] X- (CH2) n-SiY3
[0110] Wherein
[0111] X is an organic functional group, including but not limited to amino groups (-NH) , mono (C1-C4-) alkyl amino groups, di (C1-C4-) alkyl amino groups, preferably amino-, monomethylamino-, dimethylamino-, diethylamino-, and di-n-butylamino-groups, more preferably amino-groups. etc., n is an integer of 1-3, preferably 2 or 3, and especially 3, and
[0112] Y is an (C1-C4-) alkoxy functional group attached to silicon, including but not limited to methoxy groups, ethoxy groups, n-butoxy groups, preferably methoxy groups or ethoxy groups.
[0113] Typical examples are 3-Aminopropyltrimethoxysilane (e.g., CAS No. 13822-56-5) and 3-Aminopropyltriethoxysilane (e.g., CAS No. 919-30-2) , preferably 3-Aminopropyltriethoxysilane.
[0114] Another type of E3) Alkoxy Aminoalkylsilanes are the compounds of the formula
[0115] X- (CH2) n-SiYmZ3-m
[0116] Wherein
[0117] X, Y, and n are defined as above, m is an integer of 1-3, preferably 1 or 2, and very preferably 1, Z is the functional group of (C1-C4-) alkyl, including but not limited to methyl, ethyl, n-butyl, preferably methyl or ethyl, very preferably methyl.
[0118] Typical examples are 3- (Dimethoxymethylsilyl) propylamine (e.g., CAS No. 3663-44-3) and 3-Aminopropylmethyldiethoxysilane (e.g. CAS No. 3179-76-8) .
[0119] The organosilicon compounds are present in the coolants RTU according to this invention, then in amounts of 0.01 to 2.0 wt%, preferably 0.01 to 1.0 wt%, more preferably 0.05 to 1.0 wt%, even more preferably 0.05-0.5 wt%, for example, 0.05wt%, 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, and 0.5wt%. Especially preferred ranges are from 0.05 to 0.4 wt%, preferably from 0.05 to 0.3 wt%, more preferably from 0.05 to 0.2 wt%, and even more preferably from 0.1 to 0.2 wt%.
[0120] (F) Carboxylic acids
[0121] The coolants according to the present invention may further comprise, preferably do further comprise at least one aliphatic, cycloaliphatic or aromatic monocarboxylic acid (F1) , dicarboxylic or tricarboxylic acid (F2) or in the form of alkali metal, ammonium or substituted ammonium salts thereof having from 3 to 21 carbon atoms in the acid part.
[0122] (F1) aliphatic, cycloaliphatic or aromatic, preferably aliphatic or aromatic, and very preferably aliphatic monocarboxylic acids having in each case from 3 to 16 carbon atoms, or in the form of alkali metal, ammonium or substituted ammonium salts.
[0123] (F2) aliphatic or aromatic dicarboxylic or tricarboxylic acids, preferably dicarboxylic acids, even more preferably aliphatic dicarboxylic acids having in each case from 3 to 21 carbon atoms or in the form of alkali metal, ammonium or substituted ammonium salts.
[0124] Possible linear or branched aliphatic or cycloaliphatic, preferably aliphatic monocarboxylic acids of group (F1) are, for example, propionic acid, pentanoic acid, hexanoic acid, cyclohexylacetic acid, n-octanoic acid, 2-ethylhexanoic acid, n-nonanoic acid (pelargonic acid) , isononanoic acid, decanoic acid, neodecanoic acid, undecanoic acid or dodecanoic acid. Suitable aromatic monocarboxylic acids of group (F1) are in particular benzoic acid and also, for example, C1-C8-alkylbenzoic acids such as o-, m-or p-methylbenzoic acid or p-tert-butylbenzoic acid, hydroxyl-comprising aromatic monocarboxylic acids such as o-, m-or p-hydroxybenzoic acid or p- (hydroxymethyl) benzoic acid or halobenzoic acids such as o-, m-or p-fluorobenzoic acid.
[0125] As used herein, isononanoic acid refers to one or more branched-chain aliphatic carboxylic acids with 9 carbon atoms. Embodiments of isononanoic acid used in the engine coolant composition may include 7-methyloctanoic acid (e.g., CAS Nos. 693-19-6 and 26896-18-4) , 6, 6-dimethylheptanoic acid (e.g., CAS No. 15898-92-7) , 3, 5, 5-trimethylhexanoic acid (e.g., CAS No. 3302-10-1) , 3, 4, 5-trimethylhexanoic acid, 2, 5, 5-trimethylhexanoic acid, 2, 2, 4, 4-tetramethylpentanoic acid (e.g., CAS No. 3302-12-3) and combinations thereof. In a preferred embodiment, isononanoic acid has as its main component greater than 90%of one of 7-methyloctanoic acid, 6, 6-dimethylheptanoic acid, 3, 5, 5-trimethylhexanoic acid, 3, 4, 5-trimethylhexanoic acid, 2, 5, 5-trimethylhexanoic acid, and 2, 2, 4, 4-tetramethylpentanoic acid. The balance of the isononanoic acid may include other nine carbon carboxylic acid isomers and minor amounts of one or more contaminants. In a preferred embodiment, the isononanoic acid has as its main component greater than 90%of 3, 5, 5-trimethylhexanoic acid and even more preferably, the main component is greater than 95%3, 5, 5-trimethylhexanoic acid. Preferred are octanoic acid, n-nonanoic acid (pelargonic acid) , and isononanoic acid.
[0126] Typical examples of dicarboxylic or tricarboxylic acids, preferably dicarboxylic acids, more preferably aliphatic dicarboxylic acids of group (F2) are malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid (decanedioic acid) , undecanedioic acid, dodecanedioic acid, cyclopentadienedicarboxylic acid, terephthalic acid, phthalic acid and triazinetriiminocarboxylic acids such as 6, 6', 6"- (1, 3, 5-triazine-2, 4, 6-triyltriimino) trihexanoic acid. Among these the aliphatic individuals are especially preferred. Preferred are sebacic acid (decanedioic acid) and adipic acid .
[0127] The abovementioned carboxylic acids (F) are usually present entirely or predominantly as alkali metal, ammonium or substituted ammonium salts, as defined above, even when they are to have been added as free acids in the production of the antifreeze concentrate of the invention since the concentrate normally has a pH of from 4 to 11, in particular from 7 to 11, more preferably from 7 to 10, even more preferably from 7.5 to 9.5. Components (F) used as free carboxylic acids are usually converted by means of sodium or potassium hydroxide, ammonia or appropriate amines into the desired salts, preferably by means of sodium or potassium hydroxide.
[0128] In one embodiment at least one aliphatic monocarboxylic acid is present in the coolants according to the invention.
[0129] In another embodiment at least one aliphatic dicarboxylic acid is present in the coolants according to the invention.
[0130] In a preferred embodiment a combination of at least one aliphatic mono-and at least one aliphatic dicarboxylic acid is present in the coolants according to the invention.
[0131] (G) Organic amine
[0132] The coolants according to the present invention may further comprise, preferably do further comprise at least one organic amine (G) .
[0133] The amines (G) preferably have 2 to 9, especially 4 to 8 carbon atoms, preferably tertiary amines. The amines (G) preferably contain 0 to 3 ether oxygen atoms or 0 to 3, preferably 0 to 2 hydroxyl groups. Typical examples of amines (G) are ethylamine, propylamine, iso-propylamine, n-butylamine, iso-butylamine, sec. -butylamine, tert. -butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, 2-ethylhexylamine, n-nonylamine, iso-n-propylamine, diiso-propylamine, di-n-butylamine, mono-, di-and triethanolamine, mono-, di-and triisopropanolamine, C4-C10-alkyl diethanolamine, C1-C10-alkyl diisopropanolamine, piperidine, morpholine, cyclohexylamine, aniline and benzylamine. Aliphatic and cycloaliphatic amines (G) are usually saturated.
[0134] In a preferred embodiment amines (G) comprise at least one 2-hydroxyethyl-or 2-hydroxypropyl-group, more preferably at least one 2-hydroxyethyl-group.
[0135] Preferred amines (G) comprise one, two or three 2-hydroxyethyl-or 2-hydroxypropyl-groups, preferably two or three 2-hydroxyethyl-or 2-hydroxypropyl-groups, very preferably two or three 2-hydroxyethyl-groups.
[0136] Preference is given to amines (G) selected from the group consisting of diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, C4-C10-alkyl diethanolamine, C1-C10-alkyl diisopropanolamine, especially preferentially selected from the group consisting of triethanolamine, diisopropanolamine, C4-C8-alkyl diethanolamine, C1-C4-alkyl diisopropanolamine, especially preferentially selected from the group consisting of triethanolamine, diisopropanolamine, N-methyl diisopropanolamine, N-butyl diethanolamine and N-octyl diethanolamine.
[0137] Preferred are N-methyl diisopropanolamine and triethanolamine.
[0138] (H) Other additives
[0139] It is possible to add further typical coolant additives to the coolants of the present invention.
[0140] As further customary assistants, the inventive coolant may also comprise, in customary small amounts, defoamers (generally in amounts of from 0.001 to 0.01%by weight) and, for reasons of hygiene and safety in the event that it is swallowed, and bitter substances (for example of the denatonium benzoate type, generally in amounts of from 0.005 to 0.02%by weight) .
[0141] Furthermore, the coolants may comprise dyes (generally in amounts of from 0.001 to 0.005%by weight) and hard water stabilisers (generally in amounts of from 0.1 to 0.5%by weight) , e.g. based on polyacrylic acid, polymaleic acid, acrylic acid-maleic acid copolymers, polyvinylpyrrolidone, polyvinylimidazole, vinylpyrrolidone-vinylimidazole copolymers and / or copolymers of unsaturated carboxylic acids and olefins.
[0142] Composition
[0143] The composition of the coolants (Ready to use, “RTU” ) according to present invention are as follows:
[0144] (A) 45 to 65 wt%of at least one antifreezing agent, preferably 50 to 60, more preferably 50 to 55 wt%
[0145] (B) 30 to 50 wt%water, preferably 35 to 50, more preferably 40 to 50 wt%,
[0146] (C1) 0 to 0.5 wt%of at least one 2-thiothiazole of the general formula (I) , preferably 0.02 to 0.4, more preferably 0.05 to 0.2 wt%, and / or
[0147] (C2) 0.01 to 0.75 wt%of at least one azol derivative different from (C1) , preferably 0.02 to 0.5, more preferably 0.05 to 0.25 wt%,
[0148] (D) 0 to 0.75 wt%of at least one inorganic salt as further corrosion inhibitor, preferably 0.001 to 0.75wt%, more preferably 0.001 to 0.5wt%, even more preferably 0.001 to 0.3 wt%,
[0149] (E) 0.01 to 2 wt%at least one organosilicon compound, preferably 0.05 to 1.5wt%, more preferably 0.05 to 1.0 wt%,
[0150] (F) 0 to 2 wt%at least one aliphatic, cycloaliphatic or aromatic monocarboxylic, dicarboxylic or tricarboxylic acid, preferably 0.001 to 2 wt%, more preferably 0.005 to 1.0 wt%, even more preferably 0.005 to 0.5 wt%, and
[0151] (G) 0 to 2.0 wt%of at least one organic amine, preferably 0.01 to 2.0 wt%, more preferably 0.02 to 1.75wt%, more preferably 0.02 to 1.0 wt%, even more preferably 0.02 to 0.5 wt%,
[0152] (H) optionally other additives selected from the group consisting of defoamers, bitter substances and hard water stabilisers,
[0153] with the proviso that the sum of all components always add up to 100 wt%, and
[0154] with the proviso that at least one of compounds (C2) and / or (C1) is present.
[0155] The coolants RTU as described are usually destined for use at the end user, i.e. for refilling of the cooling system of vehicles.
[0156] Coolants usually are obtained from coolant concentrates by dilution with water (B) . Therefore, another subject matter of the present invention is coolant concentrates which usually contain little or no water (B) :
[0157] The composition of the coolant concentrates according to present invention are as follows:
[0158] (A) 80 to 95 wt%of at least one antifreezing agent, preferably 80 to 90wt%, more preferably 85 to 95 wt%
[0159] (B) 0 to 10 wt%water, preferably 0 to 8, more preferably 0 to 5 wt%,
[0160] (C1) 0 to 1.0 wt%of at least one 2-thiothiazole of the general formula (I) , preferably 0.04 to 0.8 wt%, more preferably 0.1 to 0.4 wt%, and / or
[0161] (C2) 0.02 to 1.5 wt%of at least one azol derivative different from (C1) , preferably 0.04 to 1.0 wt%, more preferably 0.1 to 0.5 wt%,
[0162] (D) 0 to 1.5 wt%of at least one inorganic salt as further corrosion inhibitor, preferably 0.002 to 1.5 wt%, more preferably 0.002 to 1.0 wt%, even more preferably 0.002 to 0.6 wt%,
[0163] (E) 0.1 to 4.0 wt%at least one organosilicon compound, preferably 0.1 to 3.0 wt%, more preferably 0.1 to 2.0 wt%,
[0164] (F) 0 to 4.0 wt%at least one aliphatic, cycloaliphatic or aromatic monocarboxylic, dicarboxylic or tricarboxylic acid, preferably 0.01 to 4.0wt%, more preferably 0.01 to 3.0wt%, even more preferably 0.01 to 2.0 wt%, and
[0165] (G) 0 to 4.0 wt%of at least on organic amine, preferably 0.02 to 4.0wt%, more preferably 0.02 to 2.0wt%, even more preferably 0.02 to 1.0 wt%,
[0166] with the proviso that the sum of all components always add up to 100 wt%, and
[0167] with the proviso that at least one of compounds (C2) and / or (C1) is present.
[0168] Coolants are usually obtained from the concentrates by dilution with water (B) in the ratio 1: 0.75 to 1: 1.5 (v / v) .
[0169] A further embodiment of the present invention are coolant super concentrates. Coolant concentrates usually are obtained from coolant super concentrates by dilution with the glycol (A) , respectively coolants may be obtained from coolant super concentrates by dilution with the glycol (A) and water (B) . Hence, the coolant super concentrates usually contain little or no water (B) and less glycol than the concentrates. In the concentrates or super concentrates glycol (A) acts as a solvent for the other constituents and, therefore, may be present in higher amounts.
[0170] The composition of the coolant super concentrates according to present invention are as follows:
[0171] (A) 20 to 90 wt%of at least one antifreezing agent, preferably 30 to 85, more preferably 40 to 80 wt%
[0172] (B) 0 to 10 wt%water, preferably 0 to 8, more preferably 0 to 5 wt%,
[0173] (C1) 0 to 1.5 wt%of at least one 2-thiothiazole of the general formula (I) , preferably 0.06 to 1.4, more preferably 0.15 to 0.6 wt%, and / or
[0174] (C2) 0.03 to 2.25 wt%of at least one azol derivative different from (C1) , preferably 0.06 to 1.5, more preferably 0.15 to 0.75 wt%,
[0175] (D) 0 to 2.25 wt%of at least one inorganic salt as further corrosion inhibitor, preferably 0.01 to 1.5 wt%, more preferably 0.01 to 1.5 wt%, even more preferably 0.01 to 0.9 wt%,
[0176] (E) 0.5 to 6.0 wt%at least one organosilicon compound, preferably 0.5 to 5.0wt%, more preferably 0.6 to 5.0 wt%,
[0177] (F) 0 to 6 wt%at least one aliphatic, cycloaliphatic or aromatic monocarboxylic, dicarboxylic or tricarboxylic acid, preferably 0.05 to 6wt%, more preferably 0.05 to 4.0 wt%, even more preferably 0.05 to 3.0 wt%, and
[0178] (G) 0 to 6.0 wt%of at least on organic amine, preferably 0.1 to 6.0wt%, more preferably 0.1 to 4.0wt%, more preferably 0.1 to 3.0 wt%, even more preferably 0.1 to 2.0 wt%,
[0179] with the proviso that the sum of all components always add up to 100 wt%, and
[0180] with the proviso that at least one of compounds (C2) and / or (C1) is present.
[0181] It is an advantage of the present coolants and coolant compositions that they exhibit not only low electrical conductivity but also a high inhibition of corrosion, especially corrosion of ferrous-and aluminium-containing alloys, and non-ferrous-alloys.
[0182] In addition, present coolants and coolant compositions according to the invention have high tolerance to residues of fluoroaluminate fluxes in soldered aluminium radiators and cooling plates, i.e. good compatibility with flux. In other words, the Si-containing coolant shows no Si-depletion in the presence of flux.
[0183] For some time, the cooling apparatus or cooling circuits for ICE and NEV which are usually used in vehicle and automobile construction but also for stationary engines have been made predominantly or solely of aluminium or aluminium alloys. Specific soldering processes, for example soldering under a protective gas atmosphere, are used here. In such soldering processes, the concomitant use of a flux is necessary. Here, potassium fluoroaluminates are usually used as flux, for example a mixture of KAlF4, K2AlF5 and K3AlF6 (for example commercially available under the name ) .
[0184] Part of the fluxes mentioned remains on the surface of the cooling apparatus after the soldering operation. These flux residues in the cooling apparatus lead more or less quickly to precipitation of aluminium hydroxide gels and thus to sludge formation in the cooling circuit after introduction of aqueous coolant compositions and operation of the engine due to a chain of chemical reactions, which are in equilibrium with one another, with the water and the constituents of the aqueous coolant compositions. This greatly restricts the effectiveness of heat removal from the (electric) engine and as a consequence also the functions of the heat exchange for the heating system, cooling of the air supply and gearbox oil cooling. In addition, the presence of aluminium hydroxide gels has an adverse effect on the corrosion protection provided by the coolant because the corrosion protection action is considerably reduced as a result of adsorption of the corrosion inhibitors on the aluminium hydroxide gels.
[0185] As a matter of fact, the adoption of flux in NEV is even more widespread and significant compared to ICE due to the large scale application of cooling plates for battery thermal management. These cooling plates are normally made of Aluminium alloys, placed outside and / or inside of battery pack in which coolant flow through the channels to remove the heat generated by battery pack. More specifically, the cooling plates are made by soldering process under a protective gas atmosphere in which flux is indispensable.
[0186] There is a demand for coolant compositions which have a high tolerance to residues of fluoroaluminate fluxes in soldered aluminium radiators and cooling plates, i.e. which no longer tends, or tends to a significantly less extent, to form precipitates of aluminium hydroxide gels and formation of sludge in the cooling circuit and thus makes more effective corrosion protection possible.
[0187] Therefore, it is even more advantageous that present coolants and coolant compositions further have high tolerance to residues of fluoroaluminate fluxes in soldered aluminium radiators and cooling plates, i.e. good compatibility with flux.
[0188] Therefore, another aspect of the present invention is the use of the coolants according to the present invention in cooling systems with ICE, battery, E-motors, control unit for automobiles and stationary platforms as well. The cooling systems are at least partly, preferably predominantly or solely made of aluminium or aluminium alloys.
[0189] For the use in internal combustion engines (ICE) , it is advantageous to have at least the optional compounds (D) and (F) present in the coolants, preferably the compounds (D) , (F) , and (G) .
[0190] Therefore, a preferred embodiment of the present invention concerns the use of coolants, comprising
[0191] (A) at least one antifreezing agent selected from the group consisting of 1, 2-ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, glycerol, dimers, trimers or oligomers thereof, and mono-or dialkyl ethers thereof
[0192] (B) water
[0193] (C2) at least one azol derivative different from (C1) ,
[0194] (C1) optionally additionally to azol derivative (C2) at least one 2-thiothiazole of the general formula (I)
[0195] where the variable R1 is a carboxyalkyl radical of the formula - (CmH2m) -COOX, where m is from 1 to 4 and X is hydrogen, an alkali metal cation, an ammonium cation or a substituted ammonium cation, and the variables R2 and R3 are each, independently of one another, hydrogen or a C1-C4-alkyl group, where R2 and R3 together with the two ring carbon atoms of the thiazole ring to which they are attached may also form a five-or six-membered saturated or unsaturated ring,
[0196] (D) at least one inorganic salt as further corrosion inhibitor selected from the group consisting of molybdates, borates, silicates, vanadates, tungstates, inorganic phosphate salts, and antimonates, preferably molybdates or phosphates, more preferably molybdates,
[0197] (E) at least one organosilicon compound, comprising at least one alkoxy aminoalkylsilane (E3) and optionally additionally at least one further organosilicon compound selected from the group consisting of
[0198] -esters of orthosilicic acid (E1) and
[0199] -alkoxy alkylsilanes (E2) ,
[0200] (F) at least one aliphatic, cycloaliphatic or aromatic monocarboxylic, dicarboxylic or tricarboxylic acid as acid or in the form of alkali metal, ammonium or substituted ammonium salts thereof having from 3 to 21 carbon atoms in the acid part, and
[0201] (G) at least one organic amine
[0202] in cooling systems with internal combustion engines.
[0203] In a preferred embodiment, the amount of compound (E3) for this respective use is at least 0.1 wt%, preferably 0.1 to 0.4 wt%, more preferably from 0.1 to 0.3 wt%, even more preferably from 0.1 to 0.2 wt%.
[0204] The electrical conductivity is reduced compared to the coolants according to EP 2956520 B1 with simultaneous retention of their anti-corrosion activity.
[0205] Examples
[0206] If not mentioned otherwise electrical conductivity was determined according to ASTM D 1125 at 25 ℃ in μS / cm throughout the text. Equipment used is METTLER TOLEDO Seven Direct SD30.
[0207] Glassware corrosion tests according to ASTM D1384 or equivalent Chinese National Standard GB 29743.1-2022 and GB 29743.2-20XX (published in Jan. 2024 for public opinion) .
[0208] GB 29743.1-2022 is a mandatory national standard in China for coolant application that serves to determine the corrosion susceptibility of Cast iron, Aluminum, Steel, Solder, Copper and Brass in cooling apparatus for ICE. Six metal coupons are assembled together in a fixed sequence. Put the assembled metals set into the prepared coolant solution for test at a temperature of 88℃. After testing, all metal coupons are processed by a described method and the weight change is determined by weighing, corrosion rate is given in mg / coupon.
[0209] Corrosion test according to GB 29743.1-2022 / ASTM D1384 was carried out in 33.3%aqueous solution for 336 hrs with air in the presence of "corrosive water" according to test procedure.
[0210] GB 29743.2-20XX (published in Jan. 2024 for public opinion) is another national standard in China for coolant application that serves to determine the corrosion susceptibility of Aluminum, Steel, Aluminium alloys, Copper and Brass in cooling apparatus for NEV. Seven metal coupons are assembled together in a fixed sequence. Put the assembled metals set into the prepared coolant solution for test at a temperature of 80℃. After testing, all metal coupons are processed by a described method and the weight change is determined by weighing, corrosion rate is given in mg / coupon. Corrosion test according to GB 29743.2-20XX was carried out in 33.3%aqueous solution for 336 hrs with air in the presence of "corrosive water" according to test procedure.
[0211] Flux compatibility test was carried out in the procedure similar to ASTM D1384, whereas six pieces of metal coupons are all Al coupons, with air flow 6 L / h at a temperature of 60 ℃ for 168 h. Test fluid is 50%RTU with the addition of 300 ppm of flux. After testing, check the fluid and Al coupons appearance, measure the Si ions concentration in the post-test fluid.
[0212] Examples of RTU coolants according to the present invention are listed in Table 1. In addition, pure water / glycol fluid, a commercialized LECC with a freezing point of -40℃ and one coolant contains tetraethoxysilane (TEOS) (compound (E1) ) as the solo organosilicon compound (without the presence of compound (E3) ) were used as Comparative Examples 1, 2 and 3 that are presented in Table 2.
[0213] The coolants further comprise commercially available defoamer, hard water stabiliser, dyes, and bitter substance.
[0214] Key Components information:
[0215] 3-Aminopropyltriethoxysilane (APTES) , 3-Aminopropyltrimethoxysilane (APTMS) and Triethyl ortho silicate (TEOS) were purchased from Sinopharm Chemical Reagent Co., Ltd..
[0216] Table 2 Comparative examples Ready-To-Use compositions *) As 50%RTU aqueous solution.
[0217] Table 3 Glassware corrosion test results according to GB 29743.2-20XX
[0218] Table 4 Glassware corrosion test according to ASTM D1384 / GB 29743.1-2022 and GB 29743.2-20XX of Example 1
[0219] Table 5 Glassware corrosion test according to ASTM 1384 / GB 29743.1-2022 and GB 29743.2-20XX of Example 2
[0220] As can been seen from the above results shown in Table 3, the inventive examples show great metal protection properties under such a harsh test condition considering the electrical conductivity is less than 110 μs / cm.
[0221] More importantly, the results from Table 4 and Table 5 surprisingly and unexpectedly show that both Examples 1 and 2 can not only meet GB 29743.2-20XX spec, but also can meet ASTM 3306 / GB 29743.1-2022 spec simultaneously. In another word, both two examples according to the present invention with a low electrical conductivity characteristic can meet NEV GB spec as well as ICE GB spec.
[0222] Table 6 Flux compatibility testing results
[0223] Results from Table 6 clearly show that Example 1, 3, 5, 6 & 7 is better than Example 2, 4 and 8 in terms of flux compatibility because of the formation of gel in the test which deprives silicon-containing compounds from the coolant (Flux compatibility tests of comparative examples1, 2 and 3 were not carried out due to these three comparative examples are unqualified to meet corrosion test spec) .
[0224] In addition, the Al metal coupons of Example 1 looked bright and shiny after testing while the coupons in other Examples were dull, and the coupons in Examples 2 & 8 even became stained and dull. Another most obvious difference is liquid appearance after testing. Indeed, liquid was clear and no gel formation of Example 1, 3, 5, 6 & 7 while strong gel formed of Example 2, 4 and 8 and liquid got turbid.
[0225] Si concentration is another indicator of the flux compatibility for both examples. High Si concentration is expected to ensure long term anti-corrosion performance. For example, in theory, Si concentration in Example 1 is 130 ppm, theoretical value of Si in Example 2 is 260 ppm. From the results in Table 6, it shows that there is almost no depletion in Si level when no TEOS was used (i.e. examples 1, 3, 5, 6 & 7) .For this reason, no gel formation.
Claims
1.Coolants, comprising(A) at least one antifreezing agent selected from the group consisting of 1, 2-ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, glycerol, dimers, trimers or oligomers thereof, and mono-or dialkyl ethers thereof(B) water(C2) at least one azol derivative different from (C1) ,(C1) optionally additionally to azol derivative (C2) at least one 2-thiothiazole of the general formula (I)where the variable R1 is a carboxyalkyl radical of the formula - (CmH2m) -COOX, where m is from 1 to 4 and X is hydrogen, an alkali metal cation, an ammonium cation or a substituted ammonium cation, and the variables R2 and R3 are each, independently of one another, hydrogen or a C1-C4-alkyl group, where R2 and R3 together with the two ring carbon atoms of the thiazole ring to which they are attached may also form a five-or six-membered saturated or unsaturated ring,(D) optionally at least one inorganic salt as further corrosion inhibitor selected from the group consisting of molybdates, borates, silicates, vanadates, tungstates, inorganic phosphate salts, and antimonates,(E) at least one organosilicon compound, comprising at least one alkoxy aminoalkylsilane (E3) and optionally additionally at least one further organosilicon compound selected from the group consisting of- esters of orthosilicic acid (E1) and- alkoxy alkylsilanes (E2) ,(F) optionally at least one aliphatic, cycloaliphatic or aromatic monocarboxylic, dicarboxylic or tricarboxylic acid as acid or in the form of alkali metal, ammonium or substituted ammonium salts thereof having from 3 to 21 carbon atoms in the acid part, and(G) optionally at least one organic amine.2.Coolants according to Claim 1, comprising(A) 45 to 65 wt%of at least one antifreezing agent,(B) 30 to 50 wt%water,(C1) 0.0 to 0.5 wt%of at least one 2-thiothiazole of the general formula (I) ,(C2) 0.01 to 0.75 wt%of at least one azol derivative different from (C1) ,(D) 0.0 to 0.75 wt%of at least one inorganic salt as further corrosion inhibitor,(E) 0.01 to 2 wt%at least one organosilicon compound,(F) 0.0 to 2 wt%at least one aliphatic, cycloaliphatic or aromatic monocarboxylic, dicarboxylic or tricarboxylic acid, and(G) 0.0 to 2.0 wt%of at least one organic amine;(H) optionally other additives selected from the group consisting of defoamers, bitter substances and hard water stabilisers,with the proviso that the sum of all components always add up to 100 wt%.3.Coolants according to any one of the preceding claims, wherein the coolants further comprise at least one of the compounds (D) , (F) and (G) , preferably the coolants further comprise the compounds (D) and (F) , more preferably the coolants further comprise the compounds (D) , (F) and (G) .4.Coolants according to any one of the preceding claims, wherein the electrical conductivity according to ASTM D 1125 at 25 ℃ of the coolant as 50%RTU aqueous solution is from 5 to 500 μS / cm, preferably from 5 to 200 μS / cm, more preferably from 5 to 100 μS / cm .5.Coolants according to any one of the preceding claims, wherein the antifreezing agent (A) is selected from the group consisting of 1, 2-ethylene glycol and 1, 2-propylene glycol, preferably 1, 2-ethylene glycol.6.Coolants according to any one of the preceding claims, wherein the 2-thiothiazole of the general formula (I) (C1) is selected from the group consisting of (2-benzo-thiazylthio) acetic acid and 3- (2-benzothiazylthio) propionic acid or an alkali metal, ammonium or substituted ammonium salt thereof.7.Coolants according to any one of the preceding claims, wherein at least one azol derivative (C2) different from (C1) is present and is selected from the group consisting of benzotriazole, tolutriazole (tolyltriazole) , and hydrogenated tolutriazole, preferably selected from the group consisting of benzotriazole and tolutriazole.8.Coolants according to any one of the preceding claims, wherein the at least one inorganic salt (D) is selected from the group consisting of molybdates, silicates, borates, vanadates, tungstates and inorganic phosphate salts, preferably selected from the group consisting of molybdates, silicates, borates, inorganic phosphate salts and vanadates, more preferably selected from the group consisting of molybdates, inorganic phosphate salts, and silicates, and especially are molybdates.9.Coolants according to any one of the preceding claims, wherein compound (E) is at least one alkoxy aminoalkylsilane (E3) without the presence of any further silicon-containing compounds.10.Coolants according to any one of the claims 1 to 8, wherein compound (E) is at least one alkoxy aminoalkylsilane (E3) in combination with an ester of orthosilicic acid (E1) .11.Coolants according to any one of the preceding claims, wherein the at least one carboxylic acid comprises at least one aliphatic monocarboxylic acid, preferably selected from the group consisting of 2-ethylhexanoic acid, n-octanoic acid, n-nonanoic acid (pelargonic acid) , and isononanoic acid.12.Coolants according to any one of the preceding claims, wherein the at least one carboxylic acid comprises at least one aliphatic dicarboxylic acid, preferably selected from the group consisting of adipic acid and sebacic acid / decanedioic acid.13.Coolants according to any one of the preceding claims, wherein a combination of at least one aliphatic monocarboxylic acid and at least one aliphatic dicarboxylic acid is present.14.Coolants according to any one of the preceding claims, wherein organic amine (G) is selected from the group consisting of diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, C4-C10-alkyl diethanolamine, C1-C10-alkyl diisopropanolamine, especially preferentially selected from the group consisting of triethanolamine, diisopropanolamine, C4-C8-alkyl diethanolamine, C1-C4-alkyl diisopropanolamine.15.Use of coolants according to any one of the preceding claims in cooling systems with ICE, battery, E-motors, control unit for automobiles and stationary platforms as well.16.Use according to Claim 15, wherein the cooling system is at least partly, preferably predominantly or solely made of aluminium or aluminium alloys.
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